Stabilizing Crystal Framework of an Overlithiated Li_1+xMn₂O₄ Cathode by Heterointerfacial Epitaxial Strain for High-Performance Microbatteries

Abstract

To meet the increasing demands of high-energy and high-power-density lithium-ion microbatteries, overlithiated Li 1+ x Mn 2 O 4 (0 ≤ x ≤ 1) is an attractive cathode candidate due to the high theoretical capacity of 296 mAh g –1 and the interconnected lithium-ion diffusion pathways. However, overlithiation triggers the irreversible cubic-tetragonal phase transition due to Jahn–Teller distortion, causing rapid capacity degradation. In contrast to conventional lithium-ion batteries, microbatteries offer the opportunity to develop specific thin-film-based modification strategies. Here, heterointerfacial lattice strain is proposed to stabilize the spinel crystal framework of an overlithiated Li 1+ x Mn 2 O 4 (LMO) cathode by epitaxial thin film growth on an underlying SrRuO 3 (SRO) electronic conductor layer. It is demonstrated that the lattice misfit at the LMO/SRO heterointerface results in an in-plane epitaxial constraint in the full LMO film. This suppresses the lattice expansion during overlithiation that typically occurs in the in-plane direction. It is proposed by density functional theory modeling that the epitaxial constraint can accommodate the internal lattice stress originating from the cubic-tetragonal transition during overlithiation. As a result, a doubling of the capacity is achieved by reversibly intercalating a second lithium ion in a LiMn 2 O 4 epitaxial cathode with a complete reversible phase transition. An impressive cycling stability can be obtained with reversible capacity retentions of above 90.3 and 77.4% for the 4 and 3 V range, respectively. This provides an effective strategy toward a stable overlithiated Li 1+ x Mn 2 O 4 epitaxial cathode for high-performance microbatteries.

Chemical pre-lithiation of LiMn2O4 balances the low first cycle efficiency of silicon anodes

“…The presence of the tetragonal L2MO spinel phase leads to additional capacity at ∼3.0 V vs. Li/Li + where the occupation of Li transitions from octahedral sites (16c) to tetrahedral sites (8a), which arises from the transition to a lack of Jahn–Teller distortions in the cubic spinel LMO phase. 34–36 During subsequent discharge down to 3.0 V vs. Li/Li + , the cubic phase LMO will not electrochemically convert back to the tetragonal phase L2MO, thus enabling the ability to tune ICE.…”